Methods and compositions for preparing rigid foams with non-chlorofluorocarbon blowing agents

ABSTRACT

Disclosed are methods and compositions for preparing rigid foams by contacting a polyisocyanate with a polyol mixture comprising 
     (a) from about 40-95% by weight of a polyester or polyether polyol; 
     (b) a catalytic amount of a catalyst system comprising a primary catalyst and an amino acid salt catalyst derived from sarcosine; and 
     (c) a non-chlorofluorocarbon blowing agent.

This is a division of application Ser. No. 08/238,388, filed May 5,1994.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is in the field of rigid foams and the method forproduction of such foams. More particularly it relates to spray foamsand pour-in-place foams and the methods for preparing such foams.

2. Description of the Prior Art

Rigid foams have been employed for a variety of uses including, forexample, insulating the roofs of buildings, as insulation for solid orliquid containing tanks, doors, water heaters, and picnic coolers.

Several fully halogenated hydrocarbons (chlorofluorocarbons, commonlyreferred to as CFC's) normally used as blowing agents for thepreparation of rigid foams are believed to cause environmental problems.For instance, CFC-11 (trichlorofluoromethane) and CFC-12(dichlorodifluoromethane) have been implicated in the deterioration ofthe stratospheric ozone layer. Thus, there has been much effort inresearch for developing alternative blowing agents that may (partly orwholly) replace the halogenated hydrocarbons as blowing agent in thestandard foam formulations. The result is the use of a variety ofnon-chlorofluorocarbons (non-CFCs) as blowing agents.

When rigid foams have been prepared by reacting polyisocyanates withmixtures of polyols containing non-CFCs in the presence of trimerizationcatalysts such as potassium octanoate, the results in many instanceshave not produced rigid foams with properties as good as those blownwith CFC's.

Among the problems associated with these reactions is an excessiveamount of heat generated during the reaction of the polyol mixture withthe polyisocyanate leading to relatively high pressures in the foam asthe polymerization occurs. The high pressures are undesirable since theycause spray foam to "creep" as it cures. The high pressures also lead tothe presence of "pinholes" in the exterior surface of the cured sprayfoam. Cured spray foams having pinholes cannot be treated with acoating.

In conventional pour-in-place rigid foams, the high pressure produced bythe heat of the foam reaction after cure can create deformation of orwithin a molded part. Accordingly, there is a need for non-CFC blownfoams that do not produce excessive pressures which result in creepand/or distortion of the foam.

DESCRIPTION OF THE INVENTION

The invention provides rigid spray and pour-in-place foams havingimproved parallel compressive strengths, i.e., parallel compressivestrengths at least about 20% greater than in traditionally catalyzedrigid foam systems.

The rigid spray and pour-in-place foams of the invention have improvedtensile strengths, i.e., parallel tensile strengths at least about 20%greater than in traditionally catalyzed rigid foam systems.

The invention further provides rigid spray foams having improved shearstrengths i.e., parallel shear strengths at least about 20% greater thanin traditionally catalyzed rigid foam systems.

The invention encompasses rigid foams substantially free from pinholes.

It further provides rigid foams that cure substantially free from creepand distortion.

Accordingly, the invention encompasses rigid foams having urea orurethane groups as the major recurring polymer unit, the polymerscomprising the reaction product obtained by contacting a polyisocyanatewith a polyol mixture comprising

(a) from about 40-95% by weight of a polyester and/or polyether polyol;and

(b) a catalytic amount of a catalyst system comprising a primarycatalyst and a secondary catalyst comprising an amino acid salt derivedfrom sarcosine.

The invention also encompasses methods for preparing a rigid foam havingurea or urethane groups as the major recurring polymer unit comprisingcontacting a polyisocyanate with a polyol mixture comprising

(a) from about 40-95% by weight of a polyester or polyether polyol; and

(b) a catalytic amount of a catalyst system comprising a primarycatalyst and a secondary catalyst comprising an amino acid salt derivedfrom sarcosine.

It further provides polyol mixtures comprising

(a) from about 40-95% by weight of a polyester or polyether polyol;

(b) a catalytic amount of a catalyst system comprising a primarycatalyst and a secondary catalyst comprising an amino acid salt derivedfrom sarcosine; and

(c) a non-chlorofluorocarbon blowing agent.

In this document, all temperatures will be stated in degrees Celsius.All amounts, ratios, concentrations, proportions and the like will bestated in weight units, unless otherwise stated, except for ratios ofsolvents, which are in volume units.

By OH value is meant hydroxyl value, a quantitative measure of theconcentration of hydroxyl groups, usually stated as mg KOH/g, i.e., thenumber of milligrams of potassium hydroxide equivalent to the hydroxylgroups in 1 g of substance.

By NCO/OH index is meant the molar ratio, multiplied by 100, ofisocyanate groups to hydroxyl groups (including those contributed bywater) in the reaction between the polyol blend and the polyisocyanate.

By functionality is meant the number of reactive groups, e.g., hydroxylgroups, in a chemical molecule.

In the foams and methods according to the invention, the polyol mixturecomprises from about 45-80%, preferably from about 45-55%, by weight ofa polyester polyol. The polyol mixtures of the invention may furthercomprise a polyether polyol. Typical polyol mixtures comprise from about40-80%, preferably from about 45-55%, by weight of a polyether polyol.

By non-chlorofluorocarbon (non-CFC) blowing agent is meant any blowingagent capable of being employed in methods for preparing rigid foamsthat is not completely substituted by a mixture of chlorine andfluorine. I.e., perfluorinated hydrocarbons such as perfluoropentane areacceptable non-CFC's. Representative CFC's are, for example,trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12).

The polyisocyanate starting components used according to the presentinvention include aliphatic, cycloaliphatic, araliphatic, aromatic andheterocyclic polyisocyanates, such as those described, for example, byW. Siefken in Justus Liebigs Annalen der Chemie 562: 75-136. Examplesinclude ethylene diisocyanate; tetramethylene-1,4-diisocyanate,hexamethylene-1,6-diisocyanate; dodecane-1,12-diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and 1,4-diisocyanate andmixtures of these isomers;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (GermanAuslegeschrift No. 1,202,785, U.S. Pat. No. 3,401,190);hexahydrotolylene-2,4- and 2,6-diisocyanate and mixtures of theseisomers; hexahydrophenylene-1,3- and/or -1,4-diisocyanate;perhydrodiphenylmethane-2,4'- and/or 4,4'-diisocyanate; phenylene1,3-and -1,4-diisocyanate; tolylene-2,4- and -2,6-diisocyanate and mixturesof these isomers; diphenylmethane-2,4'- and/or -4,4'-diisocyanate;naphthylene-1,5-diisocyanate; triphenyl methane-4,4',4"-triisocyanate;polyphenyl-polymethylene polyisocyanate which may be obtained byaniline/formaldehyde condensation followed by phosgenation and whichhave been described, for example, in British Pat. Nos. 874,430 and848,671; m- and p-isocyanatophenyl sulphonyl isocyanate according toU.S. Pat. No. 3,454,606; perchlorinated aryl polyisocyanate asdescribed, for example, in U.S. Pat. No. 3,277,138; polyisocyanate;containing carbodiimide groups as described in U.S. Pat. No. 3,152,162;the diisocyanates described in U.S. Pat. No. 3,492,330; polyisocyanatescontaining allophanate groups as described, for example, in British Pat.No. 994,890, Belgian Pat. No. 761,626 and Published Dutch Patentapplication No. 7,102,524; polyisocyanates containing isocyanurategroups as described, for example, in U.S. Pat. No. 3,001,973, in GermanPat. Nos. 1,022,789; 1,222,067 and 1,027,394 and in GermanOffenlegungsschriften Nos. 1,929,034 and 2,004,048; polyisocyanatescontaining urethane groups as described, for example, in Belgian Pat.No. 752,261 or in U.S. Pat. No. 3,394,164; polyisocyanates containingacrylated urea groups according to German Pat. No. 1,230,778;polyisocyanates containing biuret groups as described, for example, inU.S. Pat. Nos. 3,124,605 and 3,201,372; and in British Pat. No. 889,050;polyisocyanates prepared by telomerization reactions as described, forexample in U.S. Pat. No. 3,654,016; polyisocyanates containing estergroups as mentioned, for example, in British Pat. Nos. 965,474 and1,072,956, in U.S. Pat. No. 3,567,763 and in German Pat. No. 1,231,688;reaction products of the above-mentioned isocyanates with acetalsaccording to German Pat. No. 1,072,385; and, polyisocyanates containingpolymeric fatty acid groups as described in U.S. Pat. No. 3,455,883.

The distillation residues obtained from the commercial production ofisocyanates and which still contain isocyanate groups may also be used,optionally dissolved in one or more of the above-mentionedpolyisocyanates. Mixtures of the above-mentioned polyisocyanates mayalso be used.

The polyisocyanates which are readily available are generally preferred,for example, toluene-2,4- and -2,6-diisocyanate and mixtures of theseisomers ("TDI"); polyphenyl polymethylene polyisocyanates which may beobtained by aniline/formaldehyde condensation followed by phosgenation("crude MDI"); and, polyisocyanates containing carbodiimide groups,urethane groups, allophanate groups, isocyanurate groups, urea groups orbiuret groups ("modified polyisocyanates").

A presently preferred polyisocyanate is methylene bis(phenylisocyanate).

In a typical rigid spray foam application, the polyisocyanate mixture isreacted with a polyol blend at from about a 0.85:1 to 3:1 (v/v) ratio. Apreferred ratio of polyisocyante to polyol blend is 1:1 (v/v). TheNCO/OH index in reactions according to the invention is less than about249, preferably from about 150 to 225, and more preferably from about190 to 210. The reaction can be achieved using a spray gun apparatus orother suitable mixing devices.

Starting polyol components used in the polyol blends or mixturesaccording to the present invention include polyesters containing atleast two hydroxyl groups, as a rule having a molecular weight of from300 to 10,000, in particular polyesters containing from 2 to 8 hydroxylgroups, preferably those having a molecular weight of from 350 to 700,more preferably from 350 to 600, wherein the acid component of thesepolyesters comprise at least 50%, by weight, preferably at least 70%, byweight, of phthalic acid residues.

These polyesters containing hydroxyl groups include for example,reaction products of polyhydric, preferably dihydric and optionallytrihydric, alcohols with phthalic acids and other polybasic, preferablydibasic, carboxylic acids. Instead of using the free phthalic acids orpolycarboxylic acids, the corresponding acid anhydrides or correspondingacid esters of lower alcohols or mixtures thereof may be used forpreparing the polyesters. Orthophthalic acids, isophthalic acids and/orterephthalic acids may be used as the phthalic acid. The optionalpolybasic-carboxylic acids may be aliphatic, cycloaliphatic, aromaticand/or heterocyclic and may be substituted, for example, with halogenatoms and/or may be unsaturated. The following are mentioned asexamples; succinic acid, adipic acid, suberic acid, azelaic acid,sebacic acid, trimellitic acid, tetrahydrophthalic acid anhydride,hexahydrophthalic acid anhydride, endomethylene tetrahydro phthalic acidanhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride,fumaric acid, dimeric and trimeric fatty acids, such as oleic acid,optionally mixed with monomeric fatty acids. Suitable polyhydricalcohols include, for example, ethylene glycol, propylene glycol-(1,2)and -(1,3), diol-(1,8), neopentyl glycol, cyclohexane dimethanol(1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propane diol, glycerol,trimethylolpropane, hexanetriol-(1,2,6) butane triol-(1,2,4),trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol,methylglycoside, also diethylene glycol, triethylene glycol,tetrathylene glycol, polyethylene glycols, dibutylene glycol, andpolybutylene glycols. The polyesters may also contain carboxyl endgroups. Polyesters of lactones, such as ε-caprolactone, orhydroxycarboxylic acids, such as ω-hydroxycaproic acid, may also beused.

According to the present invention, polyethers containing at least one,generally from 2 to 8, preferably 3 to 6, hydroxyl groups and having amolecular weight of from 100 to 10,000 of known type may be used in thepolyol blend. These are prepared, for example, by the polymerization ofepoxides, such as ethylene oxide, propylene oxide, butylene oxide,tetrahydrofuran, styrene oxide, or epichlorohydrin, either on its ownfor example in the presence of BF₃, or by chemical addition of theseepoxides, optionally as mixtures or successively, to starting componentshaving reactive hydrogen atoms, such as alcohols or amines, for examplewater, ethylene glycol, propylene glycol-(1,3) or -(1,2), trimethylolpropane, 4,4-dihydroxy diphenylpropane aniline, ammonia ethanolamine orethylene diamine. Sucrose polyethers which have been described, forexample in German Auslgeschrift Nos. 1,176,358 and 1,064,938 may also beused according to the present invention.

Among the corresponding polythioethers which may also be used are thecondensation products obtained from thiodiglycol on its own and/or withother glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acidsor aminoalcohols should be particularly mentioned. The products obtainedare polythio mixed ethers, polythio ether esters or polythio ether esteramides, depending on the co-components.

Polyhydroxyl compounds already containing urethane or urea groups andmodified or unmodified natural polyols, such as castor oil,carbohydrates or starch may also be used. Addition products of alkyleneoxides and phenyl/formaldehyde resins or of alkylene oxides andurea/formaldehyde resins are also suitable according to the presentinvention.

Representatives of these compounds which may be used according to thepresent invention have been described, for example, in High Polymers,Volume XVI, "Polyurethanes, Chemistry and Technology", by Saunders andFrisch, Interscience Publishers, New York; London, Volume I, 1962, pages32-42 and pages 44 to 54 and Volume II, 1964, pages 5 and 6 and 198-199,and in Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich, 1966, for example, on pages 45 to 71.

The methods and compositions of the invention are applicable topreparing rigid foams using a variety of non-CFC blowing agents.Suitable blowing agents include, but are not limited to, halogenatedhydrocarbons such as, for example, 2,2-dichloro-2-fluoroethane(CFC-141b), water, and hydrocarbons such as pentane. Other suitableorganic blowing agents include, for example, acetone, ethyl acetate,halogenated alkanes, such as methylene chloride, chloroform, ethylidenechloride, vinylidene chloride, and also butane, hexane, heptane ordiethylether. The effect of a blowing agent may also be obtained byadding compounds which decompose at temperatures above room temperatureto liberate gases, such as nitrogen, for example, azo compounds, such asazoisobutyric acid nitrile. Other examples of blowing agents and detailsabout the use of blowing agents may be found in Kunststoff-Handbuch,Volume VII, published by Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich,1966, for example, on pages 108 and 109, 453 to 455 and 507-510.

Compounds which readily initiate a polymerization reaction of theNCO-groups at temperatures as low as room temperature are used as theprimary catalyst system for polymerization. Compounds of this type aredescribed, for example, in French Pat. No. 1,441,565, Belgian Pat. Nos.723,153 and 723,152 and German Pat. No. 1,112,285.

Such catalyst systems are, in particular, mononuclear or polynuclearMannich bases of condensable phenols, oxo-compounds and secondary amineswhich are optionally substituted with alkyl groups, aryl groups oraralkyl groups, preferably those in which formaldehyde is used as theoxo-compound and dimethylamine as the secondary amine. More or lesslarge proportions of carbodiimide structures generally occur in theforms, as shown by IR spectoscopy, depending on conditions, especiallythe reaction temperature attained.

Other suitable primary catalysts are the salts of the alkali metals oralkaline earth metals of carboxylic acids and phenols, such as, forexample, potassium octoate. The quantity of the primary polymerizationcatalyst is essentially determined by the type (and if necessary thebasicity) of the catalyst; i.e., from 0.1 to 100%, by weight, preferablyfrom 0.3 to 29%, by weight, of catalyst in relation to the isocyanatemay be used.

According to the present invention, the conventional catalysts that maybe used as the primary catalyst for the polyurethane reaction include,for example, tertiary amines, such as triethylamine, tributylamine,N-methyl morpholine, N-ethylmorpholine, N-cocomorpholine,N,N,N',N'-tetramethylethylenediamine, 1,4-diaza-bicyclo-(2,2,2)-octane,N-methyl-N'-dimethyl aminoethylpiperazine, N,N-dimethylbenzylamine,bis-(N,N-diethylaminoethyl)adipate, N,N-diethylbenzylamine,pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine,N,N,N',N'-tetramethyl-1,3-butanediamine,N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole and2-methylimidazole.

Tertiary amines containing isocyanate-reactive hydrogen atoms used asprimary catalysts include, for example, triethanolamine,triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine,N,N-dimethylethanolamine and the reaction products thereof with alkyleneoxides, such as propylene oxide and/or ethylene oxide.

Silaamines having carbon-silicon bonds as described, for example, inGerman Pat. No. 1,229,290 (corresponding to U.S. Pat. No. 3,620,984) mayalso be used as catalysts, for example, 2,2,4-trimethyl-2-silamorpholineand 1,3-diethylaminomethyl-tetramethyldisiloxane.

The primary catalysts used may also be basic nitrogen compounds, such astetralkylammonium hydroxides, alkali metal hydroxides, such assodium-hydroxide, alkali metal phenolates, such as sodium phenolate, oralkali metal alcholates, such as sodium methylate. Hexahydrotriazinesmay also be used as catalysts. Any of the primary catalysts derived fromamines may be used in the invention as the corresponding ammonium saltsor quaternary ammonium salts.

According to the present invention, organic metal compounds, inparticular organic tin compounds, may also be used as catalysts.

Suitable organic tin compounds are preferably tin(II)-salts ofcarboxylic acids, such as tin(II)-acetate, tin(II)-octoate,tin(II)-ethylhexoate and tin(II)-laurate, and the tin(IV)-compounds, forexample dibutyl tin oxide, dibutyl tin dichloride, dibutyl tindiacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tindiacetate.

Suitable organo lead compounds for use as primary catalysts include leadnaphthanate and lead octoate.

All of the above-mentioned primary catalysts may be used as mixtures.

Further representatives of primary catalysts which may be used accordingto the present invention, as well as details on the mode of operation ofthe catalyst are described in Kunststoff-Handbuch, Volume III, publishedby Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example, onpages 96 to 102.

Presently preferred primary catalysts include N,N-dimethylcyclohexylamine, lead naphthanate, tin octanoate and tin dilaurate.

The primary catalysts are generally used in a quantity of from about0.001 to 10%, by weight, based on the quantity of the polyesters usedaccording to this invention.

According to the present invention, surface-active additives, such asemulsifiers and foam stabilizers, may also be used. Suitable emulsifiersinclude, for example, the sodium salts of ricinoleic sulphonates, orsalts of fatty acids and amines, such as oleic acid diethylamine orstearic acid diethanolamine. Alkali metal or ammonium salts of sulphonicacids, such as dodecyl benzene sulphonic acid or dinaphthylmethane;disulphonic acid or of fatty acids, such as ricinoleic acid, or ofpolymeric fatty acids may also be used as surface-active additives.

The foam stabilizers used are mainly polyether siloxanes, especiallythose which are water-soluble. These compounds generally have apolydimethyl siloxane group attached to a copolymer of ethylene oxideand propylene oxide. Foam stabilizers of this type have been described,for example, in U.S. Pat. Nos. 2,834,748; 2,917,480 and 3,629,308.

According to the present invention, it is also possible to use knowncell regulators such as paraffins or fatty alcohols or dimethylpolysiloxanes, as well as pigments or dyes and known flame-proofingagents, for example, trischloroethylphosphate, tricresylphosphate orammonium phosphate or polyphosphate, also stabilizers against ageing andweathering, plasticizers, fungistatic and bacteriostatic substances andfillers, such as barium sulphate, kieslguhr, carbon black or whiting.

Other examples of surface-active additives, foam stabilizers, cellregulators, reaction retarders, stabilizers, flame-proofing substances,plasticizers, dyes, fillers and fungistatic and bacteriostaticsubstances which may also be used according to the present invention anddetails concerning the use and action of these additives may be found inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich 1966, for example on pages 103 and 113.

The secondary catalysts, i.e., amino acid salt catalysts, suitable foruse in the invention include those derived from sarcosine. Suitableamino salts derived from sarcosine include various N-(2-hydroxy or2-alkoxy-5-alkylphenyl)alkyl sarcosinates. The alkyl groups areindependently C₁ -C₁₈ alkyl groups and the alkoxy groups are C₁ -C₆alkoxy groups. Of course, each of the sarcosinate derivatives includes asuitable counterion, such as, for example, sodium, potassium, magnesium,lithium, etc. A presently preferred amino acid salt is sodiumN-(2-hydroxy-5-nonylphenyl)methyl sarcosinate. Each of the amino acidderivatives may be prepared according to the procedures set forth inU.S. Pat. No. 3,903,018. Representative amino acid salt catalysts are,for example, sodium N-(2-hydroxy-5-methylphenyl)methyl sarcosinate;sodium N-(2-hydroxy-5-ethylphenyl)methyl sarcosinate; sodiumN-(2-hydroxy-5-butylphenyl)methyl sarcosinate; sodiumN-(2-hydroxy-5-heptylphenyl)methyl sarcosinate; sodiumN-(2-hydroxy-5-nonylphenyl)methyl sarcosinate; sodiumN-(2-hydroxy-5-dodecylphenyl)methyl sarcosinate; potassiumN-(2-hydroxy-5-nonylphenyl)methyl sarcosinate; lithiumN-(2-hydroxy-5-nonylphenyl)methyl sarcosinate; and mixtures thereof.Other suitable secondary catalysts include, for example, the disodiumsalt of 2,6-bis-(N-carboxymethyl-N-methylaminomethyl)p-ethylphenol andthe disodium salt of2,6-bis-(N-carboxymethyl-N-methylaminomethyl)-p-nonylphenol; andmixtures thereof.

The amino acid salt catalyst is typically employed in the polyol blendor mixture in amounts of from about 0.1 to about 5.0 percent, andpreferably from about 0.75 to about 2.0 percent, based on the totalpolyol composition. At least an effective or catalytic amount of theamino acid salt should be present. By an "effective amount" or catalyticamount is meant a sufficient quantity to permit cure of the foam. Acured spray foam has a compressive strength of at least about 15lbs./in². within about 5 minutes after the foam is sprayed. A curedpour-in-place foam can be demolded without distortion within about 5minutes of filling the mold.

The compositions prepared according to the invention for use in sprayapplications may be applied with spray guns such as, for example, a "D"spray gun, a Probler Air-Purge spray gun, or a Gusmer Corp. GX-7 spraygun in the standard setup. Suitable metering devices for use with sprayguns include, for example, the Gusmer H2, H3, H2000 and VR 3000, and theGrayco Foamcap 400 series metering machines.

The foams obtained in accordance with the present invention may be used,for example, as insulating materials, in the construction industry, thecommercial sector, as constructional materials, or the recreationalindustry as well as in the furniture industry. Examples of uses forfoams prepared according to the invention include doors, water heaters,picnic coolers, etc.

All documents, e.g., patents and journal articles, cited above or beloware hereby incorporated by reference in their entirety.

One skilled in the art will recognize that modifications may be made inthe present invention without deviating from the spirit or scope of theinvention. The invention is illustrated further by the followingexamples which are not to be construed as limiting the invention orscope of the specific procedures described herein.

EXAMPLE 1

Polyol mixtures for preparing spray foams are prepared by first addingthe polyester polyol to a suitable reaction vessel. After initiatingmixing, the polyether polyol, tris(chloropropyl)phosphate, epoxy resin,surfactant, water, lead naphthanate, and catalysts are added in order.The reaction vessel is then sealed. To the vessel is then added theblowing agent, 2,2-dichloro-2-fluoroethane, while maintaining thetemperature of the mixture at about 20° C. The mixture is then mixed forabout 45 minutes, and can be stored or immediately used to prepare arigid foam.

    ______________________________________                                                  Polyol Formulation                                                            1            2            3                                         Component   pbw.sup.1                                                                            %.sup.2 pbw  %     pbw  %                                  ______________________________________                                        PS 2352.sup.3                                                                             72.6   50.93   72.4 50.52 72.6 49.93                              R-470X.sup.4                                                                              27.4   19.22   27.4 19.07 27.4 18.84                              AKZO PCF.sup.5                                                                            10.68  7.49    10.68                                                                              7.43  10.68                                                                              7.35                               epoxy resin.sup.6                                                                         0.55   0.39    0.55 0.38  6.85 0.38                               L-6701.sup.7                                                                              2.74   1.92    2.74 1.91  2.74 1.88                               lead naphthanate                                                                          0.35   0.25    1.50 1.04  1.20 0.83                               sarcosine   3.00   2.10    3.00 2.09  5.00 3.44                               derivative.sup.8                                                              polycat-8.sup.9                                                                           0.5    0.35    0.50 0.35  0.50 0.34                               water       0.23   0.16    0.23 0.16  0.23 0.16                               HCFC-141b.sup.10                                                                          24.5   17.19   24.5 17.05 24.50                                                                              16.85                              ______________________________________                                                  Polyol Formulation                                                            4            5            6                                         Component   pbw    %       pbw  %     pbw  %                                  ______________________________________                                        PS 2352     72.6   49.66   72.6 49.49 72.6 49.79                              R-470X      27.4   18.74   27.4 18.68 27.4 18.79                              AKZO PCF    10.63  7.31    0.68 7.28  10.68                                                                              7.32                               Epoxy resin 0.55   0.38    0.55 0.37  0.55 0.38                               L-6701      27.74  1.87    2.74 1.87  1.35 0.93                               lead naphthanate                                                                          2.00   1.37    1.50 1.02  3.00 2.06                               sarcosine   5.00   3.42    5.00 3.41  5.00 3.43                               derivative                                                                    potassium octoate                                                                         --     --      1.00 0.70  --   --                                 polycat-8   0.50   0.34    0.50 0.34  0.50 0.34                               water       0.23   0.16    0.23 0.16  0.23 0.16                               HCFC-141b   24.50  16.77   24.50                                                                              16.70 24.50                                                                              16.80                              ______________________________________                                                  Polyol Formulation                                                            7            8            9                                         Component   pbw    %       pbw  %     pbw  %                                  ______________________________________                                        PS 2352     72.6   49.62   72.6 49.15 72.6 49.15                              R-470X      27.4   18.73   27.4 18.55 27.4 18.55                              AKZO PCF    10.68  7.30    10.68                                                                              7.23  10.68                                                                              7.23                               Epoxy resin 0.55   0.38    0.55 0.37  0.55 0.37                               L-6701      1.35   0.92    2.74 1.86  --   --                                 LK-443.sup.11                                                                             --     --      --   --    2.74 1.86                               lead naphthanate                                                                          3.50   2.39    3.50 2.37  3.50 2.37                               sarcosine   5.00   3.42    5.00 3.39  5.00 3.39                               derivative                                                                    polycat-8   0.50   0.34    0.50 0.34  0.50 0.34                               water       0.23   0.16    0.23 0.16  0.23 0.16                               HCFC-141b   24.50  16.74   24.50                                                                              16.59 24.50                                                                              16.59                              ______________________________________                                                  Polyol Formulation                                                            10           11           12                                        Component   pbw    %       pbw  %     pbw  %                                  ______________________________________                                        PS 2352     72.6   49.15   72.6 49.68 72.6 49.78                              R-470X      27.4   18.55   27.4 18.75 27.4 18.79                              AKZO PCF    10.68  7.23    10.68                                                                              7.31  10.68                                                                              7.32                               Epoxy resin 0.55   0.37    0.55 0.38  0.55 0.38                               L-6701      --     --      1.37 0.94  1.37 0.94                               LK-443      2.74   1.86    --   --    --   --                                 lead naphthanate                                                                          3.50   2.37    2.80 1.92  2.50 1.71                               sarcosine   5.00   3.39    5.00 3.42  5.00 3.43                               derivative                                                                    polycat-8   0.50   0.34    0.50 0.34  0.50 0.34                               water       0.23   0.16    0.23 0.16  .23  0.16                               HCFC-141b   24.50  16.59   25.00                                                                              17.11 25.00                                                                              17.14                              ______________________________________                                                  Polyol Formulation                                                            13           14           15                                        Component   pbw    %       pbw  %     pbw  %                                  ______________________________________                                        PS 2352     72.6   49.96   72.6 49.68 72.6 49.55                              R-470X      27.4   18.85   29.4 18.75 27.4 18.70                              AKZO PCF    10.68  7.35    10.68                                                                              7.31  10.68                                                                              7.29                               Epoxy resin 0.55   0.38    0.55 0.38  0.55 0.38                               L-6701      1.37   0.94    1.37 0.94  1.37 0.93                               lead naphthanate                                                                          2.50   1.72    3.30 2.26  3.7  2.53                               sarcosine   5.00   3.44    5.00 3.42  5.00 3.41                               derivative                                                                    polycat-8   0.50   0.34    0.50 0.34  0.50 0.34                               water       0.23   0.16    0.23 0.16  0.23 0.16                               HCFC-141b   24.50  16.86   24.50                                                                              16.76 24.50                                                                              16.71                              ______________________________________                                                  Polyol Formulation                                                            16           17           18                                        Component   pbw    %       pbw  %     pbw  %                                  ______________________________________                                        PS 2352     72.6   48.94   72.6 49.83 72.6 48.68                              R-470X      27.4   18.47   27.4 18.81 27.4 18.37                              AKZO PCF    10.68  7.20    10.68                                                                              7.33  10.68                                                                              7.16                               Epoxy resin 0.55   0.37    0.55 .38   0.55 0.37                               L-6701      1.37   0.92    1.37 .94   3.30 0.92                               lead naphthanate                                                                          2.50   1.69    2.50 1.72  1.37 2.21                               sarcosine   5.0    3.37    5.00 3.43  3.30 3.35                               derivative                                                                    polycat-8   0.50   0.34    0.50 0.34  5.00 0.34                               water       0.23   0.16    .60  0.41  0.23 0.15                               HCFC-141b   27.50  18.54   24.50                                                                              16.82 27.50                                                                              18.45                              ______________________________________                                                         Polyol Formulation                                                              19     20                                                  Component          pbw    pbw                                                 ______________________________________                                        PS 2352            72.64  72.60                                               R-470X             27.37  27.40                                               AKZO PCF           10.67  10.68                                               Epoxy resin        0.55   0.55                                                LK-443             1.37   1.37                                                lead naphthanate   0.48   0.48                                                potassium octoate  2.05   2.05                                                polycat-8          0.96   0.96                                                water              0.23   0.23                                                HCFC-141b          20.53  23.50                                               ______________________________________                                         .sup.1 parts by weight.                                                       .sup.2 weight percent.                                                        .sup.3 Modified diethylene glycol phthalate polyester polyol having an Oh     value of about 230-250, available from Stepan Company, Northfield,            Illinois.                                                                     .sup.4 Formaldehyde polymer with nonylphenol, reaction products with          diethanolamine and propylene oxide, available from Texaco Chemical Co.,       Bellaire, Texas.                                                              .sup.5 Tri (β-chloroisopropyl) phosphate, available from Akzo            Chemical Inc, Chicago, Illinois.                                              .sup.6 3,4-Epoxy cyclohexyl methyl3,4-epoxy cyclohexyl carboxylate.           .sup.7 Polyalkyleneoxidemethylsiloxane copolymer available from OSi           Specialties, Danbury, Connecticut.                                            .sup.8 Sodium N(2-hydroxy-5-nonylphenyl) methyl sarcosinate (50% active).     .sup.9 N,N-dimethylcyclohexyl amine, available from Air Products,             Allentown, Pennsylvania.                                                      .sup.10 2,2-dichloro-2-fluoroethane.                                          .sup.11 Non-silicone urethane foam surfactant available from Air Products     Allentown, Pennsylvania.                                                 

EXAMPLE 2

A rigid foam is prepared as follows: Formulation 14, which is preparedas described above, and methylene bis(phenylisocyanate) are dispensedinto a Gusman H2 metering machine which then dispenses equal volumes ofthe polyisocyanate and the polyol mixture to a Gusmer Corp. GX-7 spraygun. The polyol mixture and polyisocyanate combine in the nozzle of thespray gun which applies the mixture to a metal surface. Two additionallayers of the foam are applied. The foam is applied to the surface at atemperature of from about 115° to 130° F. The resulting rigid spray foamhas the following characteristics.

    ______________________________________                                        Flame spread        20                                                        Smoke index         640                                                       Closed Cell content 97%                                                       K-factor            0.136                                                     Sprayed density     3.17                                                      (lbs/ft..sup.3)                                                               Creep (in.)         0                                                         Pinholes (No./in..sup.2)                                                                          0                                                         percent volume loss after                                                                         6                                                         storage in 100% relative                                                      humidity at 158° C.                                                    Compressive Strength                                                                              53.5                                                      (lbs/ft..sup.3)                                                               Shear Strength      34.5                                                      (lbs/in..sup.2)                                                               Tensile Strength    62.8                                                      (lbs/in..sup.2)                                                               ______________________________________                                    

EXAMPLE 3

Rigid foam is prepared essentially as described above for Formulation 14but using Formulations 19 and 20. The resulting rigid spray foams havethe following characteristics. foam has the following characteristics.

    ______________________________________                                                        Foam Prepared                                                                 Using Formulation No.                                                         19      20                                                    ______________________________________                                        Flame Spread      50.3      56                                                Smoke Index       849       643                                               Closed Cell content                                                                             95.8%     96%                                               K-factor          0.143     0.136                                             Sprayed density (lbs/ft..sup.3)                                                                 2.99      3.17                                              Pinholes (No./in..sup.2)                                                                        .sup.  NA.sup.12                                                                        8                                                 Creep (in.)       NA        2.0                                               percent volume loss after                                                                       6.3       9.2                                               storage in 100% relative                                                      humidity at 158° C.                                                    Compressive Strength                                                                            32.7      35.9                                              lbs/ft.sup.3)                                                                 Shear Strength    NA        25.96                                             (lbs/in..sup.2)                                                               Tensile Strength  NA        34.26                                             (lbs/in..sup.2)                                                               ______________________________________                                         .sup.12 not available                                                    

EXAMPLE 4 Preparation of a Rigid Foam Using Water as the Blowing Agent

A polyol blend is prepared using 75 parts of a modified diethyleneglycol phthalate polyester polyol having an OH value of from about230-250 (sold by Stepan Company, Northfield, Ill., as PS 2502A), 25parts of an alkoxylated glycerine polyether polyol having an OH value offrom about 350-390 (sold by Stepan Company, Northfield, Ill., as PE3603), 7 parts of water, 1.5 parts B-8404 (silicone surfactant availablefrom Goldschmidt), 0.65 parts pentamethyl diethylene triamine (availablefrom Air Products as Polycat 5), and 0.5 parts sodiumN-(2-hydroxy-5-nonylphenyl)methyl sarcosinate. The polyol blend is addedto the resin tank of a Cannon H-100 metering machine. The isocyanatestorage tank contains methylene bis(phenylisocyanate). A shot of foam isdispensed at a NCO/OH index of about 115 into a paper cup or desiredpart and allowed to cure. The resulting foam has excellent compressivestrength and adhesion characteristics with low foaming pressure.

From the foregoing, it will appreciated that although specificembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit or scope of the invention.

What is claimed is:
 1. A polyol mixture comprising(a) from about 40-95%by weight of a polyol selected from the group consisting of polyesterpolyols, polyether polyols, and mixtures thereof; (b) a catalytic amountof a catalyst system comprising a tertiary amine catalyst and aN-(2-hydroxy or 2-alkoxy-5-alkylphenyl)alkyl sarcosinate, where thealkyl groups are independently C₁ -C₁₈ alkyl groups and the alkoxygroups are C₁ -C₆ groups; and (c) a non-chlorofluorocarbon blowingagent.
 2. A polyol mixture comprising(a) from about 45-55% by weight ofa polyester polyol; (b) from about 15-20% by weight of a polyetherpolyol; (c) from about 5-10% by weight of tri(beta-chloroisopropyl)phosphate; (d) lead naphthanate; (d) from about 1.5-5% by weight of acatalyst system comprising a tertiary amine catalyst and an amino acidsalt catalyst derived from sarcosine; and (e) a non-chlorofluorocarbonblowing agent.